Tuning the Structure and Reactivity of the [Cu₂(μ‐O)₂]²⁺ Core: Characterization of a New Bis(μ‐oxo)dicopper Complex Stabilized by a Sterically Hindered Dinucleating Bis(triazacylononane) Ligand

Ligand-induced perturbation of structure and function of a copper–dioxygen complex is revealed by structural characterization and reactivity studies of the complex shown on the right. In addition to preventing formation of a (μ-peroxo)dicopper isomer, notable effects arising from the ethylene linker between the capping ligands include discernible puckering of the [Cu2(μ-O)2]2+ unit, lengthened CuO distances, and slowed intramolecular monooxygenase reactivity compared to planar analogs lacking the tether.